EP3290544A1 - Agent de revêtement lubrifiant à base d'eau pour matériau métallique, matériau métallique traité en surface et procédé de formation de revêtement lubrifiant pour matériau métallique - Google Patents

Agent de revêtement lubrifiant à base d'eau pour matériau métallique, matériau métallique traité en surface et procédé de formation de revêtement lubrifiant pour matériau métallique Download PDF

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Publication number
EP3290544A1
EP3290544A1 EP16786201.0A EP16786201A EP3290544A1 EP 3290544 A1 EP3290544 A1 EP 3290544A1 EP 16786201 A EP16786201 A EP 16786201A EP 3290544 A1 EP3290544 A1 EP 3290544A1
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EP
European Patent Office
Prior art keywords
metal material
water
lubricating
lubricating coating
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16786201.0A
Other languages
German (de)
English (en)
Other versions
EP3290544B1 (fr
EP3290544A4 (fr
Inventor
Kenichiro Oshita
Shinobu Komiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
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Publication date
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Publication of EP3290544A1 publication Critical patent/EP3290544A1/fr
Publication of EP3290544A4 publication Critical patent/EP3290544A4/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
    • C10M113/10—Clays; Micas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
    • C10M113/16—Inorganic material treated with organic compounds, e.g. coated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C10M125/30—Clay
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/34—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
    • C10M159/06—Waxes, e.g. ozocerite, ceresine, petrolatum, slack-wax
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/402—Castor oils
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2010/04—Groups 2 or 12
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
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    • C10N2020/055—Particles related characteristics
    • C10N2020/061—Coated particles
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • C10N2040/245—Soft metals, e.g. aluminum
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    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings

Definitions

  • the present invention relates to a water-based lubricating coating agent for a metal material, which is capable of forming, in one step, a lubricating coating that has a two-layer structure of a chemical conversion coating for a lower layer and a lubricating coating for an upper layer at a metal material, in particular, a metal material surface such as iron and steel, stainless steel, aluminum, and magnesium, as well as techniques related thereto.
  • the present invention is directed to a lubricating coating agent which can be used for plastic working such as forging, wire drawing, tube drawing, and heading of the metal material, for press molding of a plate material, and in sliding parts of various devices, and further including no black-based lubricant such as molybdenum disulfide or graphite.
  • a lubricating coating agent which can be used for plastic working such as forging, wire drawing, tube drawing, and heading of the metal material, for press molding of a plate material, and in sliding parts of various devices, and further including no black-based lubricant such as molybdenum disulfide or graphite.
  • coatings that have lubricity are provided on the metal material surfaces.
  • Such coatings include a reactive type of forming, on a metal material surface, a chemical conversion coating by chemical reaction, and then further forming a lubricating coating.
  • lubricating coatings that have a two-layer structure obtained by forming, on a metal material surface, a chemical conversion coating such as a phosphate coating (target metal: iron and steel, magnesium, and the like), an oxalate coating (target metal: iron and steel, stainless steel, and the like), or an aluminum fluoride coating (target metal: aluminum) that has a role as a carrier, and then further applying a lubricant such as a lime soap, a molybdenum disulfide, or an oil, and lubricating coatings that have a three-layer structure (chemical conversion coating/metal soap coating/unreacted soap coating) obtained by applying a chemical conversion coating, and then coating with a reactive soap such as sodium stearate.
  • the latter lubricating coatings that have the three-layer structure are known to be capable of producing stable and excellent lubricity even in heavy working regions.
  • lubrication treatment methods provided with chemical conversion treatment steps have required a long treatment process as follows, and a lubrication treatment which has a short treatment process, and allows a short time treatment has been thus desired conventionally.
  • Patent Literature 1 discloses an acid lubricant containing, as its main constituents, 0.1 to 30 weight% of a water-soluble and/or water-dispersible resin, and one of emulsified and dispersed paraffins, waxes, esters of higher fatty acids, and metal soaps, or a mixture thereof in a phosphoric acid aqueous solution with a concentration of 1 to 50 weight%.
  • Patent Literature 1 JP 51-94436 A
  • Patent Literature 1 the lubricant described in Patent Literature 1 is mainly intended for hot-rolled steel sheets, and focusing on iron oxide scale removal with phosphoric acid, rather than chemical conversion treatment. Therefore, chemical conversion coatings iron phosphate are formed on the steel sheet surfaces, but because of the extremely low pH of the lubricant, and thus the excessively strong etching action on the steel sheets, it is difficult to form dense chemical conversion coatings with excellent resistance to galling, required for plastic working and press molding.
  • an object of the present invention is to provide a water-based lubricating coating agent for a metal material, capable of carrying out a chemical conversion treatment and a lubrication treatment at the same time, which makes it possible to achieve excellent lubricity even in plastic working, press molding, and the like, and at the same time, operability (e.g., process shortening, sludge reduction).
  • an acidic water-based lubricating coating agent including a specific lubricating component and chemical conversion component can achieve excellent lubricity and operability (e.g., process shortening, sludge reduction) at the same time, thereby leading to the completion of the present invention.
  • a water-based lubricating coating agent for a metal material (hereinafter, abbreviated as a lubricating coating agent) according to the present invention is an acidic lubricating coating agent obtained by blending: at least one lubricating component other than black-based solid lubricants; and a chemical conversion component derived from at least one compound selected from the group consisting of a phosphoric acid compound, an oxalic acid compound, a molybdic acid compound, a zirconium compound, and a titanium compound.
  • the concentration of the lubricating component is 5 mass% or more, more preferably 10 mass% or more in mass ratio to the mass of the total solid content in the lubricating coating agent mentioned previously.
  • the upper limit thereof is not particularly limited, but for example, 96 mass% or less.
  • the concentration of the chemical conversion component is 0.3 to 8 mass%, more preferably 0.5 to 5 mass% when the total mass (including water) of the lubricating coating agent is regarded as 100 mass%.
  • the lubricating coating agent has pH of 2.0 to 6.5, more preferably 3.0 to 6.0.
  • At least one selected from the group consisting of the following lipophilic lubricating component (A), a cleavage solid lubricant (B), and carrier particles (C) can be applied as the lubricating component mentioned previously.
  • the lubricating component more preferably includes at least the carrier particles (C).
  • the lipophilic lubricating component preferably has a solubility parameter (SP value) of 10 or less, further preferably 9 or less.
  • the layered clay mineral is preferably 40° or more, and further preferably 60° or more in water contact angle.
  • the layered clay mineral is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less in average particle size (volumetric basis) obtained by a laser diffraction method.
  • the aspect ratio in a cross section of the layered clay mineral is preferably 3 to 150, more preferably 5 to 100, further preferably 5 to 30.
  • the inclusion amount of the lipophilic lubricating component between the particles of and/or the layers of the layered clay mineral is preferably 5 mass% or more, and further preferably 8 mass% or more in mass ratio to the total mass of the carrier particles.
  • the layered clay mineral preferably has Mohs hardness of 2 or less, and further preferably 1.
  • At least one selected from a water-based inorganic salt, a water-based organic salt, and a water-based resin can be applied as a binder component for a lubricating coating.
  • a surface-treated metal material characterized in that the coating amount of a coating formed at a metal material surface with the lubricating coating agent according to the present invention (a chemical conversion coating on the metal material surface and a lubricating coating on the chemical conversion coating) is, as dried coating amounts, adapted such that the chemical conversion coating for a lower layer is formed to be 0.1 g/m 2 or more, more preferably 0.3 g/m 2 or more, whereas the lubricating coating for an upper layer is formed to be 0.5 g/m 2 or more, more preferably 3 g/m 2 or more.
  • the problem mentioned previously can be also solved by a method for forming a lubricating coating at a metal material and a method for manufacturing a surface-treated metal material, which are characterized by including a contact step of bringing a metal material surface into contact with the lubricating coating agent according to the present invention.
  • the acidic water-based lubricating coating agent including the specific lubricating component and chemical conversion component and water, the surface-treated metal material, and the method for forming a lubricating coating for a metal material are applied, thereby making it possible to carry out, in one step, a chemical conversion treatment and a lubrication treatment at the same time, also achieving a non-black color, making it possible to produce stable and excellent lubricity even in a heavy working region, and thus prevent from seizure and galling, further making it possible to improve operability such as the reduced amount of sludge accumulated in a treatment tank, and furthermore, also achieving excellent corrosion resistance.
  • a lubricating coating agent according to the present invention is an acidic water-based lubricating coating agent which is capable of forming, in one step, a chemical conversion coating for a lower layer and a lubricating coating for an upper layer, characterized in that the lubricating coating agent includes specific lubricating component and chemical conversion component, and has pH of 2.0 to 6.5.
  • the coating formation mechanism of a common chemical conversion treatment is that when a metal material is brought into contact with a chemical conversion treatment agent, the metal material surface is etched (dissolved) by H + ions as an acid component (etching component) in the chemical conversion treatment agent, thereby increasing the pH near the surface.
  • the increased pH near the surface insolubilizes ions derived from the chemical conversion component present near the surface (anions and cations produced by ionization of compounds such as phosphoric acid compounds as described later), thereby an insolubilized product as a chemical conversion coating being formed on the metal material surface.
  • At least one selected from the group consisting of a phosphoric acid compound, an oxalic acid compound, a molybdic acid compound, a zirconium compound, and a titanium compound can be used as the chemical conversion component.
  • the phosphoric acid compound for use in the lubricating coating agent according to the present invention is a soluble primary phosphate (Me(H 2 PO 4 ) n ), and at least one selected from the group consisting of Zn 2+ , Ni 2+ , Mn 2+ , Ca 2+ , Co 2+ , Mg 2+ , Al 3+ , Na + , K + , and NH 4 + can be applied for Me n+ as a cation.
  • Me(H 2 PO 4 ) n soluble primary phosphate
  • the chemical conversion coating formed from the primary phosphate is a poorly-soluble tertiary phosphate, and specifically, examples of the tertiary phosphate include Zn 3 (PO 4 ) 2 , Zn 2 Fe(PO 4 ) 2 , Zn 2 Ni(PO 4 ) 2 , Mn 3 (PO 4 ) 2 , Zn 2 Mn(PO 4 ) 2 , Mn 2 Fe(PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Zn 2 Ca(PO 4 ) 2 , and FePO 4 .
  • a chemical conversion coating of FePO 4 is formed when a metal material as a material is an iron-based material, and when at least one primary phosphate selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate is adapted as a chemical conversion component. More specifically, when the metal material as a material is an iron-based material including at least iron, iron ions eluted by an acid component (etching component) are supposed to react directly with primary phosphate ions to form FePO 4 , and the supply source for the iron ions is iron as a material. It is to be noted that the term of poor solubility is defined as a solubility of less than 0.2 g/100 g in water.
  • the use of an iron-based material as a metal material causes iron ions eluted by an acid component to react directly with oxalate ions, thereby forming a poorly-soluble iron oxalate as a chemical conversion coating.
  • the oxalic acid compound is not particularly limited as long as the compound is a soluble oxalate, at least one selected from the group consisting of an oxalic acid, a sodium oxalate, a potassium oxalate, and an ammonium oxalate, and the like can be used.
  • the chemical conversion component is a molybdic acid compound
  • a chemical conversion coating composed of a mixture of iron molybdate and molybdenum oxide is formed when an iron-based material is used as a metal material.
  • the molybdic acid compound is not particularly limited as long as the compound is a soluble molybdate, at least one selected from the group consisting of, for example, a molybdic acid, a sodium molybdate, a potassium molybdate, and an ammonium molybdate, and the like can be used.
  • the chemical conversion component is a zirconium compound
  • at least one selected from the group consisting of inorganic acid salts such as a fluorozirconic acid and a zirconium nitrate, and organic acid salts such as a zirconium acetate and a zirconium lactate can be used.
  • the chemical conversion coating formed in this case is a mixture of zirconium oxide and zirconium hydroxide.
  • the chemical conversion component is a titanium compound
  • at least one selected from the group consisting of inorganic acid salts such as a fluorotitanic acid and a titanium nitrate, and organic acid salts such as a titanium acetate and a titanium citrate can be used.
  • the chemical conversion coating formed in this case is a mixture of titanium oxide and titanium hydroxide.
  • the concentration and pH of the chemical conversion component are important.
  • the concentration of the chemical conversion component is preferably 0.3 to 8 mass%, more preferably 0.5 to 5 mass% when the total mass (including water) of the lubricating coating agent according to the present invention is regarded as 100 mass%.
  • the concentration of the chemical conversion component falls below 0.3 mass%, the decreased reactivity may reduce the coating amount of the chemical conversion coating, thereby deteriorating the lubricity.
  • the concentration of the chemical conversion component exceeds 8 mass%, the coating amount of the chemical conversion coating is sufficient, but operational problems may be caused, such as an increased amount of sludge generated.
  • the adjustment of the concentration of the chemical conversion component to 0.5 mass% or more can further enhance the lubricity of the chemical conversion coating, and the adjustment thereof to 5 mass% or lower can suppress the generation of sludge in a more reliable manner.
  • a preferred pH range is 2.0 to 6.5, more preferably 3.0 to 6.0.
  • the pH falls below 2.0, the etching ability for a metal material surface is excessive thereby making a uniform chemical conversion coating less likely to be formed, and there is a possibility of decreasing the lubricity or increasing the amount of sludge generated.
  • the pH in excess of 6.5 makes it impossible to ensure the etching amount required for the chemical conversion reaction, thus making a chemical conversion coating less likely to be formed, and the lubricity may be decreased.
  • the adjustment of the pH range to 3.0 to 6.0 can ensure a more preferred etching ability, and thus further enhance the lubricity.
  • the acid and alkali components for adjusting the pH is not particularly limited, but in the case of any chemical conversion component, it is preferable to use, as the alkali component, at least one selected from sodium hydroxide, potassium hydroxide, ammonia, and amines.
  • the acid component it is preferable to use a phosphoric acid in accordance with the chemical conversion component when the chemical conversion component is a phosphoric acid compound, and likewise, it is preferable to use an oxalic acid when the chemical conversion component is an oxalic acid.
  • the chemical conversion component is a molybdic acid compound, it is preferable to use an organic acid such as a tartaric acid, a citric acid, and an acetic acid.
  • the chemical conversion component according to the present invention is considered to include these pH adjusters also in addition to the previously mentioned chemical conversion component (at least one selected from the group consisting of a phosphoric acid compound, an oxalic acid compound, a molybdic acid compound, a zirconium compound, and a titanium compound).
  • compounds more preferred when the metal material as a material is an iron-based material include at least one phosphoric acid compound selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate, an oxalic acid, and at least one molybdic acid compound selected from the group consisting of a sodium molybdate, a potassium molybdate, and an ammonium molybdate.
  • phosphoric acid compound selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate
  • an oxalic acid an oxalic acid
  • molybdic acid compound selected from the group consisting of a sodium molybdate, a potassium molybdate, and an ammonium molybdate.
  • the reason why the previously mentioned chemical conversion component (at least one phosphoric acid compound selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate, an oxalic acid, and at least one molybdic acid compound selected from the group consisting of a sodium molybdate, a potassium molybdate, and an ammonium molybdate) is preferred will be described in terms of operability (sludge reduction). It is to be noted that in the following description, cases of using an iron-based material as a metal material for a material will be explained as examples.
  • iron ions eluted from iron as a material by etching react immediately with the phosphoric acid compound mentioned previously, thereby turning into a chemical conversion coating of iron phosphate (FePO 4 ). For this reason, almost no sludge is generated because almost no iron is eluted into the lubricating coating agent.
  • the amount of eluted iron ions incorporated in the chemical conversion coating is, although slightly, smaller as compared with the more preferred chemical conversion component mentioned previously, and the iron ions that are not incorporated in the chemical conversion coating thus turns into sludge as an iron phosphate or an iron hydroxide in the lubricating coating agent.
  • the amount of sludge is smaller, which never reaches any operationally problematic level.
  • the chemical conversion component at least one phosphoric acid compound selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate, an oxalic acid, and at least one molybdic acid compound selected from the group consisting of a sodium molybdate, a potassium molybdate, and an ammonium molybdate
  • the chemical conversion coating formed from at least one phosphoric acid compound selected from a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate is an iron phosphate (FePO 4 ).
  • the chemical conversion coating of iron phosphate is higher in coatability as compared with other phosphate coatings, and the iron phosphate is thus superior in corrosion resistance, with lubricity at a level equivalent to other phosphates.
  • a chemical conversion coating of mixed iron molybdate and molybdenum oxide is obtained from at least one chemical conversion component selected from the group consisting of a sodium molybdate, a potassium molybdate, and an ammonium molybdate.
  • This chemical conversion coating is superior particularly in corrosion resistance to other chemical conversion coatings, due to the oxidizing action of the molybdic acid included in the chemical conversion coating. It is for the foregoing reasons that the iron phosphate coating, the iron oxalate coating, and the coating composed of iron molybdate and molybdenum oxide are particularly preferred as the chemical conversion coating.
  • the coating amount required for the achievement of favorable lubricity is not obtained even with the use of, as the chemical conversion component, at least one primary phosphate selected from the group consisting of a primary sodium phosphate, a primary potassium phosphate, and a primary ammonium phosphate and at least one oxalic acid compound selected from the group consisting of an oxalic acid, a sodium oxalate, a potassium oxalate, an ammonium oxalate, and the like, because few iron ions are supplied from the material. Therefore, there is a need to use a chemical conversion component other than the foregoing chemical conversion components, more preferred chemical conversion components are molybdic acid compounds, zirconium compounds, and titanium compounds.
  • an oxidant may be added to the lubricating coating agent.
  • the type of the oxidant is not particularly limited, but at least one selected from bromates, molybdates, hydrogen peroxide, nitrites, ferric nitrate, and the like can be used.
  • the oxidant concentration in the lubricating coating agent is preferably 0.01 to 0.5 mass% when the total mass (including water) of the lubricating coating agent is regarded as 100 mass%.
  • a first lubricating component that can be used for the lubricating coating agent according to the present invention is at least one lipophilic lubricating component selected from the group consisting of an oil, an extreme-pressure agent, a soap, and a wax.
  • the lipophilic lubricating component can be referred to also as a sort of lipophilic organic lubricating component.
  • At least one selected from the group consisting of mineral oils, animal and plant oils, and synthetic oils can be used as the oil. More specifically, for example, naphthenic mineral oil or paraffinic mineral oil-based machine oils, turbine oils, spindle oils, and the like can be used as the mineral oils.
  • naphthenic mineral oil or paraffinic mineral oil-based machine oils, turbine oils, spindle oils, and the like can be used as the mineral oils.
  • palm oils, rapeseed oils, coconut oils, castor oils, beef tallow, pork oils, whale oils, fish oils, or these components with ethylene oxide added thereto for example, polyoxyethylene castor oils (ethylene oxide adducts)
  • ethylene oxide adducts polyoxyethylene castor oils (ethylene oxide adducts)
  • Ester oils for example, esters of polyhydric alcohols such as ethylene glycol and trimethylolpropane and fatty acids such as stearic acid, oleic acid, and linoleic acid (e.g., trimethylolpropane trioleate)
  • silicone oils for example, polydimethylsiloxane and polydiphenylsiloxane
  • Hydrophobic organic compounds for example, organic ammonium compounds, organic phosphonium compounds, organic sulfonium compounds, organic amine compounds
  • the naphthenic mineral oils are preferred as the mineral oils; the palm oils and the castor oils of the plant oils, and the oils with ethylene oxide added thereto (polyoxyethylene plant oils (ethylene oxide adducts)) are preferred as the animal and plant oils; and the ester oils (trimethylolpropane trioleate) are preferred as the synthetic oils.
  • an agent that effectively develops an extreme-pressure effect at the friction surface between a metal material and a tool during working is preferred as the extreme-pressure agent.
  • an extreme-pressure agent can include sulphurized olefins, sulfurized esters, sulphites, thiocarbides, phosphate esters, phosphite esters, molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), zinc dithiophosphate (ZnDTP), and tricresyl phosphate, and the phosphates (tricresyl phosphate) are preferred.
  • the ratio between the oil and the extreme-pressure agent preferably falls within the range of 1 : 0.03 to 1 : 1 in mass ratio.
  • the ratio between the oil and the extreme-pressure agent is 1 : 0.03 to 1 : 1 in mass ratio
  • the lubricity is further improved with an extreme-pressure action imparted.
  • the ratio between the oil and the extreme-pressure agent exceeds 1 : 1, the extreme-pressure action is nearly saturated.
  • the previously mentioned oil and extreme-pressure agent may be blended with a viscosity index improver for the purpose of achieving higher lubricity.
  • a viscosity index improver selected from polymethacrylates, olefin copolymers, and polyisobutylenes can be used.
  • the viscosity index (JIS K2283) is preferably 100 or more, and more preferably 200 or more.
  • an alkali metal salt of a fatty acid such as stearic acid, myristic acid, palmitic acid
  • a metal soap obtained by reacting a fatty acid (such as stearic acid, myristic acid, palmitic acid) having 12 to 26 carbon atoms and at least one metal selected from zinc, calcium, barium, aluminum, and magnesium.
  • the soap preferably has a melting point of 100 to 250°C.
  • An alkali metal salt of a stearic acid and a metal soap (zinc stearate) obtained by reacting a fatty acid having 12 to 26 carbon atoms and zinc are more preferred as the soap.
  • the wax is not to be considered particularly specified in terms of structure and type, but preferably has a melting point of 70 to 150°C, because the wax is melted by heat generated during working, thereby developing lubricity.
  • Waxes that have a melting point in this range include, for example, microcrystalline waxes, polyethylene waxes, polypropylene waxes, and carnauba waxes, and polyethylene waxes are preferred.
  • a second lubricating component that can be used for the lubricating coating agent according to the present invention is a cleavage solid lubricant (hereinafter, simply referred to as a "solid lubricant").
  • solid lubricant refers to a matter interposed between two objects for purposes such as friction reduction, seizure prevention, and improved mold life when the objects cause relative movement.
  • the solid lubricant is used as one component of a lubricating coating for plastic working, sliding members, press molding, and the like, and specifically, layered clay minerals, crystalline inorganic salts, polymer materials, soft metals, and the like are applied as the solid lubricant.
  • Examples of the solid lubricant mentioned previously, which can be used for the present invention, include inorganic salts with crystallinity (crystalline inorganic salts), that is, phosphates, sulfates, hydroxides such as zinc hydroxides and calcium hydroxides, and oxides such as zinc oxides and calcium oxides, and layered clay minerals that have a layered crystal structure, other than black-based solid lubricants (the L value in the L*a*b color system (JIS Z-8729) of a solid lubricant alone is 30 or less, which is measured with a color computer, with a petri dish (internal diameter: 85.5 mm ⁇ , height: 20 mm) filled with a solid lubricant powder through a sieve opening of 300 ⁇ m in mesh size) as typified by molybdenum disulfide and graphite.
  • inorganic salts with crystallinity crystalline inorganic salts
  • hydroxides such as zinc hydroxides and calcium hydroxides
  • the cleavage refers to the property of splitting and fracturing at a crystal face with the weakest atomic bonding force when a load is applied to a solid lubricant. This property causes, in plastic working, the solid lubricant to follow effectively to an area expansion of the worked surface during the working, thereby imparting slidability, and at the same time, preventing from galling.
  • the previously mentioned solid lubricant can be also referred to as a sort of solid inorganic lubricant, a cleavage solid lubricant, or a cleavage solid inorganic lubricant.
  • the solid lubricants mentioned previously are layered clay minerals.
  • the first reason why the layered clay minerals are preferred as a solid lubricant for the lubricating coating agent according to the present invention is because of superior lubricity, and further superior acid resistance as compared with crystalline inorganic salts.
  • the lubricating coating agent according to the present invention is acidic, and a solid lubricant that is insoluble or poorly soluble in acid is thus more preferred.
  • the previously mentioned layered clay minerals can include a smectite group of natural products and synthetic products, a vermiculite group of natural products and synthetic products, a mica group of natural products and synthetic products, a brittle mica group of natural products and synthetic products, a pyrophyllite group of natural products and synthetic products, and a kaolinite group of natural products and synthetic products.
  • These layered clay minerals may be each used alone, or more than one thereof may be used in combination.
  • Clay minerals are main-constituent minerals constituting clay, layered silicate minerals (phyllosilicate minerals), calcite, dolomite, feldspars, quartz, boiling stones (zeolite), and others, minerals that have chain-like structures (such as attapulgite, sepiolite), minerals that have no clearly crystal structure (allophane), and the like are referred to as clay minerals, and in general, layered silicate minerals among the clay minerals are referred to as layered clay minerals.
  • the layered clay mineral forms a crystal structure that has two-dimensional layers of positive and negative ions stacked parallel and bonded, and this layered structure has therein two structural units: one unit of a tetrahedral layer composed of Si 4+ and O 2- surrounding the Si 4+ ; the other of an octahedral layer composed of Al 3+ (or Mg 2+ , Fe 2+ , or the like) and (OH) - surrounding the Al 3+ .
  • tetrahedral layer In the tetrahedral layer, O located at four vertexes of the tetrahedron and Si located in the center form tetrahedrons of Si-O, which are linked to each other at the three vertexes to spread two-dimensionally, thereby forming a layer lattice that has a composition of Si 4 O 10 .
  • the Si 4+ is often substituted with Al 3+ .
  • octahedral layer octahedrons formed by (OH) or O located at six vertexes of the octahedron and Al, Mg, Fe, or the like located in the center are linked at each vertex to spread two-dimensionally, thereby forming a layer lattice that has a composition of Al 2 (OH) 6 , Mg 3 (OH) 6 , or the like.
  • the octahedral layers include: a 3-octahedral type that has lattice points all occupied with a divalent cation (such as Mg 2+ ) at the lattice point of cation surrounded by six anions; and a 2-octahedral type that has 2/3 lattice points occupied with a trivalent cation (such as Al 3+ ) at the lattice point of cation, and 1/3 lattice points remaining vacant.
  • a divalent cation such as Mg 2+
  • 2-octahedral type that has 2/3 lattice points occupied with a trivalent cation (such as Al 3+ ) at the lattice point of cation, and 1/3 lattice points remaining vacant.
  • one of the combinations is a 2 : 1 type structure that has, as a unit, a linkage of two tetrahedral layers and one octahedral layer sandwiched therebetween; and the other is a 1 : 1 type structure that has, as a unit, a linkage of one tetrahedral layer and one octahedral layer.
  • the smectite group, vermiculite group, mica group, and pyrophyllite group mentioned previously refer to layered clay minerals that have the 2 : 1 type structure
  • the kaolinite group refers to layered clay minerals that have the 1 : 1 type structure.
  • the layered clay mineral has the 1 : 1 crystal structure, which is believed to exhibit hydrophilicity due to the orientation of octahedrons with hydrophilic groups (such as OH) at the surface.
  • hydrophilic groups such as OH
  • the 2 : 1 crystal structure there is believed to be a strong tendency to be lower in hydrophilicity than the 1 : 1 structure, because of the orientation of tetrahedrons having hydrophobic groups (SiO) at the surface.
  • the smectite group includes montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, and stevensite
  • the vermiculite group includes di.vermiculite and tri.vermiculite
  • the mica group includes muscovite, palagonite, illite, phlogopite, biotite, lepidolite, and lepidolite
  • the brittle mica group includes margarite and clintonite
  • the pyrophyllite group includes pyrophyllite and talc
  • the kaolinite group includes kaolinite, dickite, nacrite, halloysite, chrysotile, lizardite, and antigorite.
  • the layered clay minerals that belong to the pyrophyllite group mentioned above are low in Mohs hardness and excellent in lipophilicity. It is to be noted that the Mohs hardness of the layered clay mineral and the relationship between lipophilicity and lubricity will be described in detail later.
  • the lubricating coating agent according to the present invention it is also possible to use, as the lubricating component, the previously mentioned lipophilic lubricating component and the previously mentioned solid lubricant each alone, but these components are used in combination as a preferred form of lubricating component.
  • the use of the solid lubricant and the lipophilic lubricating component in combination improves galling resistance and slidability, thereby making it possible to achieve higher lubricity.
  • the second reason why the layered clay minerals are preferred as a solid lubricant according to the present invention is because the layered clay minerals which have a layered structure can include the previously mentioned lipophilic lubricating component between particles of and/or between layers of the minerals. More specifically, the reason is because the inclusion of the previously mentioned lipophilic lubricating component between particles and/or between layers corresponding to cleavage faces of the previously mentioned layered clay mineral with cleavage can further enhance the cleavage of the layered clay mineral, and further cause a solid lubricant to take as a role of carrier particles for causing the lipophilic lubricating component to follow in a more efficient manner to an area expansion of the worked surface during working.
  • the layered clay mineral refers to particles of two-dimensional layered crystals stacked parallel and bonded.
  • the spaces between surfaces of the layered crystals are defined as interlayer spaces.
  • multiple primary particles may further aggregate (agglomerate) into larger secondary particles (the layered clay mineral that forms the secondary particles is referred to as an "aggregated layered clay mineral"), and in this case, the spaces between the particles are defined as inter-particle spaces.
  • Both the interlayer spaces and the inter-particle spaces are loosely bonded in a layered form, which serve as cleavage faces that are capable of including a lipophilic lubricating component according to the present invention.
  • the inclusion of the lipophilic lubricating component between the particles of and/or between the layers of the layered clay mineral with cleavage allows the layered clay mineral and the lipophilic lubricating component to follow at the same time, that is, to take a role as carrier particles, even in working which is high in working load and high in the area expansion factor of the worked surface, such as cold plastic working, thereby imparting slidability at the same time as the prevention of galling, and thus allowing for improved lubricity.
  • the previous techniques have never achieved any acidic lubricating coating agent that can cause the layered clay mineral in the lubricating coating agent to take a role as carrier particles as just described, and further form a chemical conversion coating at the same time as a lubricating coating.
  • inclusion herein means conditions that the lipophilic lubricating component is trapped between particles of and/or between layers of the layered clay mineral. More specifically, in the carrier particles according to the present invention, when the layered clay mineral is not cleaved, the lipophilic lubricating component is held between the particles of and/or between the layers of the layered clay mineral, and this condition is referred to as an "inclusion" condition according to the present invention.
  • the lipophilic lubricating component included between the particles of and/or between the layers of the layered clay mineral exudes to the worked surface, and the exudation of the lipophilic lubricating component follows along with the layered clay mineral so as to wet the worked surface.
  • the concentration of the lubricating component in the lubricating coating is 5 mass% or more, more preferably 10 mass% or more in mass ratio to the mass of the total solid content (coating component) in the lubricating coating agent.
  • the concentration of the lubricating component below 5 mass% may lead to failure to achieve expected lubricity.
  • the upper limit of the concentration of the lubricating component is not particularly limited, but for example, 96 mass% or less.
  • the parameters of the lipophilic lubricating component include a solubility parameter (SP value, unit (cal/cm 3 ) 1/2 ).
  • the solubility parameter refers to a parameter for solubility or compatibility in a two-component system.
  • the solubility or compatibility is supposed to be better as the solubility parameters of the components are closer in value to each other.
  • Various methods are disclosed for the measurement method.
  • the SP value of the lipophilic lubricating component can be evaluated by dissolving the lipophilic lubricating component in a good solvent with a known SP value, and carry out turbidimetric titration with a poor solvent that is higher in SP value than the good solvent and a poor solvent that is lower in SP value than the good solvent.
  • the SP value of water is approximately 23, and as the SP value of a target component is lower than that of water, the lipophilicity is higher.
  • the lipophilic lubricating component for use in the present invention preferably has an SP value of 10 or less, and further preferably 9 or less.
  • the SP value of the lipophilic lubricating component exceeds 10
  • the amount of the lipophilic lubricating component included between the layers of the layered clay mineral may be decreased due to decreased lipophilicity, thereby decreasing the lubricity.
  • the barrier properties against corrosive factors such as water and chlorine may be decreased, thereby decreasing the corrosion resistance.
  • the lower limit of the SP value of the lipophilic lubricating component is not to be considered particularly specified, but for example, 7 or more.
  • the layered clay mineral itself has preferably lipophilic properties between layers of and on the surface of the layered clay mineral.
  • Parameters therefor include a water contact angle.
  • the water contact angle at the surface of the layered clay mineral alone may be preferably 40° or more, further preferably 60° or more.
  • the upper limit of the water contact angle at the layered clay mineral is not to be considered particularly specified, but for example, 150° or less.
  • the combination of the lipophilic lubricating component that has an SP value of 10 or less with the layered clay mineral that is 40° or more in water contact angle can achieve the inclusion of the lipophilic lubricating component between the particles and/or between the layers in a more efficient manner, because of high mutual lipophilicity and affinity.
  • the inclusion amount of the lipophilic lubricating component is preferably 5 mass% or more, and further preferably 8 mass% or more in mass ratio to the total mass of the carrier particles. When the inclusion amount falls below 5 mass%, the lubricity during working may be decreased, thereby causing galling.
  • the upper limit of the inclusion amount of the lipophilic lubricating component is not to be considered particularly limited, but for example, 50 mass% or lower.
  • a layered clay mineral with an organic substance supported between layers of the layered clay mineral by the method described in the International Publication WO 2012/086564 A may be used as the layered clay mineral mentioned previously.
  • the organic substance can include at least one cationic organic compound (organic group + cationic group) selected from organic ammonium compounds, organic phosphonium compounds, and organic sulfonium compounds.
  • the organic group of the organic compound is not particularly limited, but preferred are straight-chain, branched-chain, and cyclic (having a cyclic group) saturated hydrocarbon or unsaturated hydrocarbon groups having 1 to 30 carbon atoms.
  • the hydrogen atoms bonded to the carbon atoms constituting the carbon chains or the carbon rings may be substituted with other substituent groups, some of the carbon atoms constituting the carbon chains or the carbon rings may be substituted with other atoms (such as O and S, for example), and furthermore, other linkages (for example, ester linkages, ether linkages) may be included between C-C chains.
  • Preferred is an organic ammonium compound composed of: an aliphatic hydrocarbon group (preferably having 1 to 30 carbon atoms) which is advantageous for friction reducing ability; and an ammonium group which is advantageous for interlayer fixing ability.
  • organic salts for use in the interlayer introduction of the organic compound.
  • Particularly preferred organic salts are quaternary ammonium chlorides from which by-product salts are easily removed by water rinsing (such as capryl trimethyl ammonium chlorides, lauryl trimethyl ammonium chlorides, stearyl trimethyl ammonium chlorides, dicapryl dimethyl ammonium chlorides, dilauryl dimethyl ammonium chlorides, and distearyl dimethyl ammonium chlorides).
  • quaternary ammonium chlorides from which by-product salts are easily removed by water rinsing such as capryl trimethyl ammonium chlorides, lauryl trimethyl ammonium chlorides, stearyl trimethyl ammonium chlorides, dicapryl dimethyl ammonium chlorides, dilauryl dimethyl ammonium chlorides, and distearyl dimethyl ammonium chlorides.
  • the layered clay mineral mentioned previously is preferably 0.5 to 30 ⁇ m, more preferably 1 to 20 ⁇ m, and further preferably 1 to 10 ⁇ m in average particle size.
  • the average particle size of 30 ⁇ m or less makes the lipophilic lubricating component likely to be included between the layer, thus improving the lubricity and the corrosion resistance.
  • the lubricity is further improved. Even when the average particle size is less than 0.5 ⁇ m, the lubricity and the corrosion resistance are favorable, and the average particle size is selected from the perspective of cost (manufacturing cost) - effectiveness (lubricity and corrosion resistance).
  • the aspect ratio in a cross section of the layered clay mineral preferably falls within the range of 3 to 150, more preferably 5 to 100, further preferably 5 to 30.
  • the aspect ratio in excess of 150 reduces the inclusion amount of the lipophilic lubricating amount, thereby possibly decreasing the lubricity and the corrosion resistance in some cases.
  • the lubricity is further improved as the aspect ratio is reduced to 150 or less, 100 or less, and 30 or less.
  • the aspect ratio falls below 3
  • the inclusion amount of the lipophilic lubricating component has no problem, but due to the layered clay mineral particles increased in thickness, the following performance of the lubricating coating may be decreased, thereby deteriorating the lubricity.
  • the average particle size of the layered clay mineral can be measured by a laser diffraction method (volumetric basis).
  • the average particle size of the layered clay mineral according to the present invention is intended for primary particles, and in order to keep as much as possible from being affected by secondary particles as aggregates of the primary particles, particle sizes are measured after enhancing redispersion (breaking secondary particles of the primary particles aggregated, thereby separating the secondary particles again into primary particles) with ultrasonic for approximately 3 to 5 minutes in advance.
  • the average particle size for substantially primary particles can be measured by eliminating as much as possible the influence of secondary particles of the primary particles aggregated. Therefore, the average particle size of the layered clay mineral according to the present invention refers to an average value on a volumetric basis for the particle sizes of the primary particles of the layered clay mineral.
  • the aspect ratio according to the present invention is supposed to be defined as an aspect ratio in a cross section of the layered clay mineral, and obtained from the following formula.
  • the layered clay mineral for use in the present invention have plate-like or scale-like particles of two-dimensionally layered crystals stacked parallel and bonded as mentioned previously, and the proportion of the length of a planar part (that is, a crystal face parallel to a cleavage face) to the thickness of the particle (the length in a direction perpendicular to the cleavage face) corresponds to the aspect ratio in a cross section of the layered clay mineral.
  • parameters for efficiently including the lipophilic lubricating component between particles of and/or between layers of the layered clay mineral are three of: (1) the lipophilicity of the layered clay mineral and the SP value of the lipophilic lubricating component; (2) inclusion method; and (3) the average particle size and aspect ratio of the layered clay mineral.
  • the lipophilicity water contact angle
  • average particle size, and aspect ratio of the layered clay mineral, and the SP value of the lipophilic lubricating component preferred ranges are adapted as mentioned previously.
  • inclusion method examples include in the case of an oil and an extreme-pressure agent that are liquid at room temperature, an method of adding the oil and the extreme-pressure agent in predetermined amounts to a powder of the layered clay mineral, and causing the mineral to include therein the oil and the agent while stirring.
  • methods for the inclusion of a soap or a wax that is solid at room temperature include a method of turning the soap or the wax into a liquid at a temperature equal to or higher than the melting point thereof, and then mixing the liquid with the layered clay mineral, thereby causing the layers to include the liquid therebetween, and a method of applying the lubricant to a metal material surface, and then putting the material in an oven kept at a temperature equal to or higher than the melting point, thereby causing the layers to include the soap or the wax therebetween during the drying.
  • mixing with the lipophilic lubricating component in an amount equal to or larger than the amount includable between the layers can interpose the lipophilic lubricating component not only between the layers, but also between the particles.
  • the lipophilicity of the layered clay mineral and the SP value of the lipophilic lubricating component as well as the average particle size and aspect ratio of the layered clay mineral are adapted to fall within the specific ranges, thereby making it possible to ensure, in a more reliable manner, that the inclusion amount of the lipophilic lubricating component into the layered clay mineral is 5 mass% or more.
  • the reduced-pressure impregnation method the method of mixing, with the layered clay mineral, a soap or a wax turned into a liquid at a temperature equal to or higher than the melting point thereof, thereby causing the particles and the layers to include the soap or the wax therebetween, or a method of applying the lubricant to a metal material surface, and then putting the material in an oven kept at a temperature equal to or higher than the melting point, thereby causing the particles and layers to include the soap or the wax therebetween during the drying is used, thereby making it possible to further increase the inclusion amount of the lipophilic lubricating component.
  • the layered clay mineral for use in the solid lubricant according to the present invention preferably has Mohs hardness of 2 or less from the perspective of lubricity. Further preferred Mohs hardness is 1. The reason is because while the solid lubricant is broken to follow in the direction of area expansion at the surface worked in plastic working or press working, there is a tendency to achieve a lower friction coefficient and better carrier property for the lipophilic lubricating component as the layered clay mineral is lower in Mohs hardness, and as a result, better lubricity is achieved.
  • the “carrier property” herein means that as a result of decreasing the friction coefficient of the layered clay mineral, the layered clay mineral is made more likely to follow in the direction of area expansion, and the lipophilic lubricating component is thus made likely to follow, along with the layered clay mineral, in the direction of area expansion at the worked surface.
  • Mohs hardness can be measured with a Mohs scale. More specifically, 10 types (10-level Mohs hardness from 1 to 10: 1 for the softest and 10 for the hardest) of minerals that differ in hardness are adopted as reference materials, thereby evaluating whether the surface of the target material is scratched by a reference material or not.
  • the reference material with higher hardness is used and evaluated until being scratched.
  • the surface is scratched, it is confirmed that the surface of the reference material is reversely scratched by the target material, thereby determining the Mohs hardness of the substance. This is because the materials can scratch each other as long as the materials have the same hardness.
  • the layered clay mineral for use in the lubricating coating agent according to the present invention are pyrophyllite that belongs to the pyrophyllite group, and talc.
  • the reason therefor is because these layered clay minerals have a water contact angle of 110°, and thus high lipophilicity, and with Mohs hardness of 1, belong to the softest layered clay minerals.
  • the lubricating component in the lubricating coating agent according to the present invention from the perspective of enhancing the lubricity, the case (1) of using only the lipophilic lubricating component mentioned previously, the case (2) of using only the solid lubricant (the crystalline inorganic salt and/or the layered clay mineral) mentioned previously, the case (3) of using the solid lubricant and the lipophilic lubricating component in combination, the case (4) of using only the carrier particles mentioned previously, the case (5) of using the carrier particles and the lipophilic lubricating component in combination, the case (6) of using the carrier particles and the solid lubricant in combination, and the case (7) of using the carrier particles, the lipophilic lubricating component, and the solid lubricant in combination are preferred, the cases (3) to (7) are more preferred, and the cases (4) to (7) of at least including the carrier particles as the lubricating component are particularly preferred. It is to be noted that the lipophilic lubricating component is not included between the particles of and
  • the lubricating coating agent for a metal material according to the present invention can be, for the achievement of higher lubricity, further blended with at least one selected from the group consisting of a water-soluble inorganic salt, a water-soluble organic salt, and a water-based resin, as a binder component for a lubricating coating. Blending the lubricating coating agent according to the present invention with these components can attach the lubricating component more strongly to metal material surfaces, thus achieving higher lubricity.
  • the water-soluble inorganic salt has at least one selected from the group consisting of sulfates, silicates, borates, molybdates, vanadates, and tungstates.
  • the water-soluble organic salt has at least one selected from the group consisting of malates, succinates, citrates, and tartrates.
  • the cations of these salts have at least one selected from the group consisting of a sodium ion, a potassium ion, a lithium ion, an ammonium ion, amines (such as ethylamine), and alkanolamines (such as monoethanolamine and diethanolamine).
  • the water-based resin that is, water-soluble or water-dispersible polymer resin
  • at least one can be selected from polymer resins of 1,000 to 1,000,000 in weight average molecular weight.
  • the water-dispersible polymer resin is preferably 0.5 to 50 ⁇ m in average particle size (volumetric basis).
  • the type of the polymer resin is not particularly limited as long as the polymer resin has coating formability, and stable solubility or dispersibility, but for example, polymer resins can be used, such as acrylic resins, urethane resins, epoxy resins, phenolic resins, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol.
  • the weight average molecular weight of the polymer resin can be measured by a gel permeation chromatography method (GPC method).
  • the average particle size of the polymer resin can be measured in the same way as the average particle size of the layered clay mineral mentioned previously.
  • any of non-ionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants can be used as a surfactant that disperses, in water, the solid lubricant according to the present invention and the oil and the extreme-pressure agent.
  • the non-ionic surfactants include, but not particularly limited thereto, for example, polyoxyethylene alkyl esters obtained from polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and/or propylene) alkyl phenyl ether, or polyethylene glycol (or ethylene oxide) and a higher fatty acid (for example, 12 to 18 carbon atoms); and polyoxyethylene sorbitan alkyl esters composed of obtained from sorbitan, polyethylene glycol, and a higher fatty acid (for example, 12 to 18 carbon atoms).
  • the anionic surfactants include, but not particularly limited thereto, for example, fatty acid salts, sulfates, sulfonates, phosphates, and dithiophosphates.
  • amphoteric surfactants include, but not particularly limited thereto, for example, amino acid-type and betaine-type carboxylates, sulfates, sulfonates, and phosphates.
  • the cationic surfactants include, but not particularly limited thereto, for example, aliphatic amine salts and quaternary ammonium salts. These surfactants can be each used alone, or two or more of the surfactants can be used in combination.
  • the concentration of the surfactant is preferably 0.5 to 20 mass% in mass ratio to the mass of the total solid content (coating component) in the lubricating coating agent.
  • the proportion of the surfactant exceeds 20 mass%, the dispersibility of the solid lubricant is improved, while the lubricating coating may become fragile, thereby decreasing the lubricity.
  • the proportion falls below 0.5 mass%, the dispersibility of the solid lubricant is worsened, thereby making it impossible to form any uniform lubricating coating.
  • a surface-treated metal material according to the present invention is characterized in that a chemical conversion coating for a lower layer is formed to achieve a coating amount of 0.1 g/m 2 or more, more preferably 0.3 g/m 2 or more, whereas a lubricating coating for an upper layer is formed to achieve a coating amount of 0.5 g/m 2 or more, more preferably 3 g/m 2 or more.
  • the set coating amount may be determined appropriately depending on the working level required. However, when the coating amounts fall below the lower limits mentioned previously, the chemical conversion coating or the lubricating coating may fail to fully coat a metal material surface depending on the roughness of the surface, and attention is thus required in terms of lubricity and corrosion resistance.
  • the upper limits are not particularly specified, but the lower chemical conversion coating has an upper limit of 3 g/m 2 , whereas the upper lubricating coating has an upper limit of 40 g/m 2 . Even when the coatings are formed in excess of the upper limits, lubricity improved enough to meet the formation can be no longer expected, which is not economical, and problems may be even caused, such as defectively even application, defective adhesion, and the production of indentation by the remaining coating.
  • the coating amount of the lower chemical conversion coating can be adjusted with the treatment temperature and the treatment time.
  • the coating amount tends to be increased as the treatment temperature is higher, and increased as the treatment time is longer. Therefore, the appropriate adjustment of the two parameters can set conditions for achieving a target coating formation amount.
  • the coating amount of the lower chemical conversion coating may be adjusted by adjusting the concentration of the chemical conversion component, and the condition for the achievement of the target coating formation amount may be set by appropriately adjusting the concentration of the chemical conversion component.
  • the upper coating amount can be adjusted with the concentration of the total solid content including the lubricating component in the lubricating coating agent. More specifically, when the total mass (including water) of the lubricating coating agent is regarded as 100 mass%, the coating amount of 0.5 g/m 2 or more can be obtained as long as the previously mentioned total solid content concentration is 3 mass% or more. The concentration lower than the foregoing concentration reduces the dried coating amount, thereby leading to failure to achieve expected lubricity in some cases.
  • the upper limit of the concentration of the total solid content is not to be considered particularly limited, but for example, 70 mass% or lower, more preferably 50 mass% or lower.
  • the concentration of the total solid content (coating component) with respect to the total mass (also including water) of the lubricating coating agent can be measured by the following method. More specifically, the lubricating coating agent is collected in a defined amount into a container made of Teflon (registered trademark), and the collection amount is weighed accurately. Thereafter, volatile components such as water are evaporated in an oven at 110°C for 2 hours, and the amount of residue (non-volatile component) is weighed accurately. The total solid content concentration is calculated from the following formula with the respective weighing values.
  • the weighing value after drying in the following formula corresponds to "the mass of the total solid content (coating component)" in calculating the concentration of the solid lubricant in the water-based lubricating coating agent.
  • total solid content concentration mass % weighing value after drying / weighing value before drying ⁇ 100
  • a method for forming a lubricating coating for a metal material according to the present invention and a method for manufacturing a surface-treated metal material according to the present invention are characterized by including a contact step of bringing a metal material into contact with the lubricating coating agent for metal materials according to the present invention.
  • examples thereof include an immersion method, a flow coating method, a spray method, brush coating, and a cathode electrolysis method.
  • the temperature and the time are important factors for adjusting the coating amount of the chemical conversion coating, the immersion method or the spray method is a more preferred method, because the method can easily control the treatment temperature and the treatment time.
  • the treatment temperature and the treatment time may be appropriately adjusted respectively within the ranges of 30 to 70°C and 15 to 300 seconds, so as to achieve a predetermined coating amount of chemical conversion coating.
  • the agent may be left at room temperature, but preferably at 60 to 150°C for 1 to 30 minutes.
  • the metal material may be brought into contact with the lubricating coating agent warmed to 50°C to 90°C.
  • the drying characteristics are improved significantly, thereby making drying possible at room temperature in some cases, and thus making it possible to reduce the thermal energy loss.
  • an electrolytic treatment may be carried out with the use of a test specimen as a cathode and of an insoluble anode such as lead or stainless steel for an anode.
  • an insoluble anode such as lead or stainless steel for an anode.
  • no sludge is generated because chemical conversion coatings can be formed without any etching reaction, and chemical conversion coatings can be formed also in the case of metal materials which are less likely to be etched, such as stainless steel.
  • the electrolysis conditions are not particularly limited, but may be adjusted appropriately within the ranges of 5 to 40 A/dm 2 and electrolysis time: 2 to 60 seconds, depending on the required coating amount of chemical conversion coating.
  • the cleanup is intended to remove oxide scale grown by annealing or the like, and various types of contamination (e.g., oil).
  • contamination e.g., oil
  • reduced wastewater treatment burdens have been desired due to environmental concerns. In this case, the absence of wastewater can be achieved just by cleaning up the metal material surface by shot blasting, and then carrying out the contact step with the use of the lubricating coating agent according to the present invention.
  • the average particle size of the solid lubricant was measured by a laser diffraction method on a volumetric basis under the following conditions after the redispersion of the solid lubricant into primary particles with ultrasonic in water for 3 minutes in advance.
  • the aspect ratio was measured only in the case of the layered clay mineral.
  • the aspect ratio was calculated from the thickness of the particle (the length in a direction perpendicular to a cleavage face) and the length of the planar part (that is, the crystal face parallel to the cleavage face) by observation of the layered clay mineral at a magnification of 3000 times with a scanning electron microscope.
  • the layered clay mineral was subjected to an organic treatment in accordance with the method described in International Publication WO 2012/086564 A .
  • the water contact angle was measured with a bed of layered clay mineral powder between two copper plates (50 ⁇ 50 mm), which was pressed at a tightening force of 100 kgf into the form of a coating.
  • An automatic contact angle meter DM-501 from Kyowa Interface Science Co., Ltd. was used for the measurement.
  • binder components used for tests.
  • the oil and the extreme-pressure agent that are liquid at room temperature
  • the oil and the extreme-pressure agent were added to the layered clay mineral in proportions equal to or larger than an includable amount (1 : 1 in mass ratio), and mixed with the use of a mortar until being homogeneous in whole, thereby resulting in the lubricating component included between particles and/or between layers. Thereafter, the excess oil and extreme-pressure adhering to the surface of the layered clay mineral were removed by immersion in boiling water for 10 minutes, and the layered clay mineral was left to dry at room temperature for 24 hours.
  • the lubricating component turned into a liquid at a temperature equal to or higher than the melting points was added to the layered clay mineral (1 : 1 in mass ratio), and mixed therewith in a mortar until becoming fully homogeneous, thereby resulting in the lubricating component included between particles and/or between layers.
  • the wax (or zinc stearate) adhering to particle surfaces was removed by immersion for 10 minutes in an oil bath warmed to a temperature equal to the melting point of the wax (or zinc stearate) or higher, thereafter, the oil on the particle surfaces was removed by immersion in boiling water for 10 minutes, and thereafter, the layered clay mineral was left to dry at room temperature for 24 hours.
  • the coating amount of the upper lubricating coating was calculated from the mass decrease of the test piece between before and after removing the lubricating coating through immersion of the test piece subjected to the lubrication treatment in boiling water for 1 hour.
  • coating amount g / m 2 test piece mass before removing - test piece mass after removing / surface area of test piece
  • the coating amount obtained when the lower chemical conversion coating was a phosphate or an oxalate was calculated from the mass decrease of the test piece between before and after removing the chemical conversion coating further through immersion of the test piece with the upper layer removed therefrom in a 5% chromic acid aqueous solution under the condition of room temperature for 30 minutes.
  • coating amount g / m 2 test piece mass before removing ⁇ test piece mass after removing / surface area of test piece
  • each metal coating amount was measured with an X-ray fluorescence analytical instrument (model: ZSX PrimusII from Rigaku Corporation), and from the value, the coating amount was calculated through the conversion to an oxide.
  • step C cathode electrolysis treatment
  • the following lubricant (in accordance with Patent Literature 1: JP 51-94436 A ) was prepared, and subjected to the lubrication treatment in accordance with the step A.
  • the coating amount of the lower chemical conversion coating and the coating amount of the upper lubricating coating are supposed as shown in Tables 4 and 5.
  • the L value was measured as appearance evaluation after the formation of the lubricating coating.
  • the water-based lubricating coating agents for metal materials according to the examples of the present invention have achieved performance at the practical level (rated as B or higher) in all of the evaluation tests.
  • comparative example 1 and comparative example 10 subjected to the phosphate + reactive soap treatment and comparative example 9 subjected to the aluminum fluoride + reactive soap treatment have achieved lubricity at the practical level, but have larger numbers of treatment steps as compared with the present invention, and also have operability rated as C.
  • comparative examples 2 as prior art have created inferior results for all of lubricity, corrosion resistance, and operability, as compared with the lubricating coating agents according to the present invention.
  • comparative examples 3 to 6 and comparative example 8 with the pH of the lubricating coating agent, the chemical conversion concentration, and the lubricating component concentration outside the scope of the present invention have failed to reach the practical level in terms of at least one evaluation item of lubricity, corrosion resistance, and operability.
  • comparative example 7 with the use of molybdenum disulfide as a solid lubricant has achieved lubricity, corrosion resistance, and operability, at the practical levels, but an appearance rated as C. From the foregoing results, the present invention can be considered to have a greater deal of potential in industry, as compared with the prior art.

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EP16786201.0A 2015-04-27 2016-03-04 Agent de revêtement lubrifiant à base d'eau pour matériau métallique, matériau métallique traité en surface et procédé de formation de revêtement lubrifiant pour matériau métallique Active EP3290544B1 (fr)

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PCT/JP2016/056764 WO2016174924A1 (fr) 2015-04-27 2016-03-04 Agent de revêtement lubrifiant à base d'eau pour matériau métallique, matériau métallique traité en surface et procédé de formation de revêtement lubrifiant pour matériau métallique

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EP1491615B1 (fr) * 2002-03-25 2016-07-20 Nihon Parkerizing Co., Ltd. Particule metallique enrobee de savon, article fabrique a partir de cette particule, agent d'enrobage lubrifiant et pellicule d'enrobage lubrifiante
US7291402B2 (en) 2002-07-23 2007-11-06 Jfe Steel Corporation Surface-treated steel sheets of good white rust resistance, and method for producing them
US7037384B2 (en) * 2003-06-23 2006-05-02 Bulk Chemicals, Inc. Lubricating chemical coating for metalworking
JP4162619B2 (ja) * 2004-03-17 2008-10-08 株式会社リコー 熱転写記録媒体、熱転写記録方法及び記録体
JP2007002330A (ja) * 2005-06-27 2007-01-11 Baoshan Iron & Steel Co Ltd 亜鉛もしくは亜鉛合金めっき鋼板用表面処理剤及び表面処理亜鉛もしくは亜鉛合金めっき鋼板
JP2010106208A (ja) * 2008-10-31 2010-05-13 Kyodo Yushi Co Ltd 塑性加工用水溶性潤滑剤及び塑性加工方法
JP5168332B2 (ja) 2010-09-24 2013-03-21 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用の表面処理液ならびに亜鉛系めっき鋼板およびその製造方法
WO2012086564A1 (fr) * 2010-12-20 2012-06-28 日本パーカライジング株式会社 Lubrifiant de traitement plastique d'un matériau métallique
JP5745035B2 (ja) * 2011-03-28 2015-07-08 日本パーカライジング株式会社 高潤滑性固体潤滑剤

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3862466A4 (fr) * 2018-10-04 2022-07-27 Nippon Steel Corporation Procédé destiné à fabriquer un tuyau métallique, et procédé destiné à laver le tuyau métallique
WO2020165035A1 (fr) * 2019-02-14 2020-08-20 Chemetall Gmbh Procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid et lubrifiant réactif approprié
US20220119730A1 (en) * 2019-02-14 2022-04-21 Chemetall Gmbh Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor
US12139690B2 (en) * 2019-02-14 2024-11-12 Chemetall Gmbh Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor
US20240425775A1 (en) * 2019-02-14 2024-12-26 Chemetall Gmbh Simplified process for the pretreatment of metallic substrates for cold forming and a reactive lubricant for this purpose
WO2021170707A1 (fr) 2020-02-25 2021-09-02 Chemetall Gmbh Procédé de prétraitement en une étape de substrats métalliques pour formage à froid de métal
WO2021170706A1 (fr) 2020-02-25 2021-09-02 Chemetall Gmbh Procédé de prétraitement en une étape de substrats métalliques pour formage à froid de métal
WO2022207901A1 (fr) 2021-04-01 2022-10-06 Chemetall Gmbh Procédé de prétraitement en une étape de substrats métalliques à des valeurs de ph non neutres pour la formage à froid de métal

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ES2963039T3 (es) 2024-03-25
TW201723161A (zh) 2017-07-01
JP2016204724A (ja) 2016-12-08
EP3290544B1 (fr) 2023-10-18
EP3290544A4 (fr) 2018-10-10
US10760029B2 (en) 2020-09-01
WO2016174924A1 (fr) 2016-11-03
CN107709610A (zh) 2018-02-16
JP6545520B2 (ja) 2019-07-17
US20180320101A1 (en) 2018-11-08
CN107709610B (zh) 2019-12-13

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